KR20200128613A - Zinc phthalocyanine halide pigment and method for producing same - Google Patents

Abstract

The process of obtaining a zinc halide phthalocyanine crude pigment by taking out and depositing the zinc halide phthalocyanine synthesized using a compound that generates an acid by reacting with water in a basic aqueous solution, and the zinc halide phthalocyanine crude pigment as a pigment. A method for producing a zinc halide phthalocyanine pigment having a step of converting.

Description

Zinc phthalocyanine halide pigment and method for producing same

The present invention relates to a zinc halide phthalocyanine pigment and a method for producing the same.

Currently, the coloring composition is used in various fields, and specific uses of the coloring composition include printing inks, paints, resin coloring agents, textile coloring agents, IT information recording coloring materials (color filters, toners, inkjets) and the like. The pigment used in the coloring composition is largely divided into a pigment and a dye, but attention is focused on organic pigments that are predominant in terms of coloring power.

The organic compounds constituting the organic pigment are aggregated with each other after synthesis, and exist in the form of an aggregate called a cru. Therefore, usually, the organic compound after synthesis cannot be used as a pigment as it is, and a pigmentation step for adjusting the particle size is performed. The aggregate (crude) of the organic compound to be pigmented in the pigmentation process is called a crude pigment, and fine organic pigments can be obtained by grinding the crude pigment by kneading or the like.

As an organic pigment, a zinc halide phthalocyanine pigment used for a green pixel part of a color filter etc. is attracting attention (for example, refer patent document 1).

International Publication No. 2018/043548 pamphlet

One of the objects of the present invention is to provide a novel method for producing a zinc halide phthalocyanine pigment that enables further refinement of pigment particles.

As a method for synthesizing zinc halide phthalocyanine, for example, a chlorosulfonic acid method and a melting method are known. In these methods, zinc halide phthalocyanine is synthesized using a compound that reacts with water to generate an acid. By precipitating the synthesized zinc halide phthalocyanine in water or an acidic solution, a crude pigment that is an aggregate of zinc halide phthalocyanine is obtained. In such a method, usually, since an acid derived from a compound that generates an acid by reacting with the water is attached to the crude pigment, washing to remove the acid adhering to the crude pigment is required before pigmentation of the crude pigment. Done. However, as a result of the investigations of the present inventors, even if the crude pigment was washed until the pH of the filtrate was equal to that of water used for washing, it became clear that the acid remained inside the crude pigment. The present invention has been achieved based on the results of such examination.

That is, one aspect of the present invention is a step of obtaining a zinc halide phthalocyanine crude pigment by taking out and depositing a zinc halide phthalocyanine synthesized using a compound that generates an acid by reacting with water in a basic aqueous solution, and the zinc halide It relates to a method for producing a zinc halide phthalocyanine pigment having a step of pigmenting a phthalocyanine crude pigment.

According to the production method of the above aspect, it is possible to suppress the inclusion of acid in the crude zinc halide phthalocyanine pigment, thereby obtaining a fine zinc halide phthalocyanine pigment. Further, in the production method of the above aspect, a zinc halide phthalocyanine pigment having a large amount of base adsorption can be obtained.

In one aspect, the concentration of the basic compound contained in the basic aqueous solution may be 1% by mass or more.

In one aspect, the basic aqueous solution may contain a hydroxide of an alkali metal or an alkaline earth metal.

In one aspect, the temperature of the basic aqueous solution may be 5 to 90°C.

In one aspect, the pH of the zinc halide phthalocyanine crude pigment may be 5.0 or more.

In one aspect, the amount of Al contained in the zinc halide phthalocyanine crude pigment may be 3000 mass ppm or less.

Another aspect of the present invention relates to a zinc halide phthalocyanine pigment having a base adsorption amount of 0.13 mol/kg or more and an Al content of 3000 mass ppm or less.

According to the zinc halide phthalocyanine pigment of the above aspect, the amount of the dispersant used in combination with the pigment can be reduced, and defects caused by mixing a large amount of the dispersant can be reduced.

According to the present invention, it is possible to provide a novel method for producing a zinc halide phthalocyanine pigment, which makes it possible to further refine the pigment particles. Further, according to the present invention, it is possible to provide a novel zinc halide phthalocyanine pigment having a large base adsorption amount and a small Al content.

Hereinafter, preferred embodiments of the present invention will be described. However, this invention is not limited at all to the following embodiment.

The manufacturing method of the zinc halide phthalocyanine pigment of one embodiment is the first to obtain a zinc halide phthalocyanine crude pigment by taking out and depositing a zinc halide phthalocyanine synthesized using a compound that generates an acid by reacting with water in a basic aqueous solution. It has a process and a 2nd process of pigmenting the said zinc halide phthalocyanine crude pigment. Here, zinc halide phthalocyanine is a compound having a structure represented by the following formula (1).

[In formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a halogen atom]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen atom, the zinc halide phthalocyanine preferably has at least one of a bromine atom and a chlorine atom, and preferably has a bromine atom. The zinc halide phthalocyanine may have only one or both of a chlorine atom and a bromine atom as a halogen atom. That is, X ¹ to X ¹⁶ in the formula (1) may be a chlorine atom or a bromine atom.

The first step includes, for example, a synthesis step of synthesizing zinc halide phthalocyanine using a compound that generates an acid by reacting with water, and a precipitation step of taking out and depositing the synthesized zinc halide phthalocyanine in a basic aqueous solution.

As a method of synthesizing zinc halide phthalocyanine using a compound that reacts with water to generate an acid, for example, a chlorosulfonic acid method, a melting method, or the like can be mentioned.

Examples of the chlorosulfonic acid method include a method of dissolving zinc phthalocyanine in a sulfur oxide-based solvent such as chlorosulfonic acid, and adding chlorine gas and bromine to the halogenated method. The reaction at this time is, for example, at a temperature of 20 to 120°C, and is carried out within a range of 3 to 20 hours. In the chlorosulfonic acid method, a sulfur oxide-based solvent such as chlorosulfonic acid is a compound that reacts with water to generate an acid. For example, chlorosulfonic acid reacts with water to generate hydrochloric acid and sulfuric acid.

As the melting method, aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides such as sodium chloride and sodium bromide, or alkaline earth metal halides (hereinafter referred to as ``alkali (earth) metal halides'') ), a method of halogenating zinc phthalocyanine with a halogenating agent in a melt of about 10 to 170° C. comprising one or a mixture of two or more compounds used as solvents during various halogenation, such as thionyl chloride. In the melting method, a compound that becomes a solvent during halogenation such as aluminum halide, titanium halide, alkali (earth) metal halide, and thionyl chloride reacts with water to generate an acid. For example, aluminum chloride reacts with water to generate hydrochloric acid.

A suitable aluminum halide is aluminum chloride. In the above method of using aluminum halide, the amount of aluminum halide added is usually at least 3 times mol, preferably 10 to 20 times mol with respect to zinc phthalocyanine.

The aluminum halide may be used alone, but if an alkali (earth) metal halide is used in combination with the aluminum halide, the melting temperature can be lowered, which is advantageous in operation. A suitable alkali (earth) metal halide is sodium chloride. The amount of the alkali (earth) metal halide to be added is preferably 1 to 15 parts by mass of the alkali (earth) metal halide per 10 parts by mass of aluminum halide within the range of producing a molten salt.

Examples of the halogenating agent include chlorine gas, sulfuryl chloride, and bromine.

The temperature of halogenation is preferably 10 to 170°C, more preferably 30 to 140°C. Further, in order to speed up the reaction rate, it is also possible to pressurize. The reaction time may be 5 to 100 hours, preferably 30 to 45 hours.

The melting method using two or more of the above compounds in combination is a zinc halide produced by adjusting the ratio of chloride, bromide, and iodide in the molten salt, or by changing the introduction amount and reaction time of chlorine gas, bromine, iodine, etc. It is preferable because the content ratio of the zinc halide phthalocyanine having a specific halogen atom composition in the phthalocyanine can be arbitrarily controlled. Further, according to the melting method, the decomposition of the raw material during the reaction is small, the yield from the raw material is more excellent, and the reaction can be carried out in an inexpensive device without using a strong acid.

In this embodiment, by optimizing the raw material input method, the catalyst species and the amount thereof, the reaction temperature and the reaction time, it is possible to obtain a zinc halide phthalocyanine having a halogen atom composition different from that of the conventional zinc halide phthalocyanine.

In the precipitation step, for example, a mixture containing a zinc halide phthalocyanine and a compound that reacts with water and generates an acid to generate an acid is introduced into a basic aqueous solution as a take-out solution, and zinc halide phthalocyanine is precipitated (precipitated). .

In the conventional method, in the precipitation step, since an acidic aqueous solution such as water or hydrochloric acid is used instead of a basic aqueous solution, an acid derived from a compound that reacts with the water to generate an acid is introduced into the precipitate, for example, Even if the precipitate is washed until the pH of the filtrate reaches the same pH as the water used for washing, the acid contained in the precipitate (such as an acid derived from a compound that generates an acid by reacting with water) is difficult to remove. The acid remains in the pigment. The cause of this is that zinc halide phthalocyanine has a long distance between the central metal, zinc, and the nitrogen atom on the isoindolin unit, and has large voids around the central metal (zinc), so that the phthalocyanine ring is formed under acidic conditions. After nitrogen is protonated, it can be considered that the counter anion (for example, chloride ion) is easily accessible to the central metal (zinc), and the counter anion and the central metal (zinc) are bonded to each other to easily take a stable structure. On the other hand, in this embodiment, in the precipitation step, since a basic aqueous solution is used, the generation of acid is suppressed or the generated acid is neutralized. Therefore, it is possible to suppress the acid from being contained in the crude zinc halide phthalocyanine pigment.

A mixture containing a zinc halide phthalocyanine and a compound that generates an acid by reacting with water contains, for example, 20 to 60 mass% of a zinc halide phthalocyanine, and 40 to 80 mass% of a compound that generates an acid by reacting with water Include.

The basic aqueous solution is an aqueous solution having basic (alkaline) properties, and is obtained, for example, by dissolving a basic compound in water. Therefore, the basic aqueous solution can be referred to as an aqueous solution containing a basic compound.

The basic compound may be a compound exhibiting basicity in an aqueous solution, for example, an alkali metal such as sodium hydroxide, potassium hydroxide, or calcium hydroxide or a hydroxide of an alkaline earth metal, an alkali metal such as sodium carbonate or potassium carbonate, or a carbonate of an alkaline earth metal, And alkali metals such as sodium hydrogen carbonate, potassium hydrogen carbonate, and calcium hydrogen carbonate, hydrogen carbonates of alkaline earth metals, alkali metals such as sodium acetate, potassium acetate, and calcium acetate, acetates of alkaline earth metals, and ammonia. Among these, for example, in the melting method, aluminum-containing components such as aluminum hydroxide, which can be used as inorganic coagulants, are easily removed, and from the viewpoint of suppressing the aggregation of pigments and the generation of acids more suppressing pKb A compound having 5 or less is preferable, and a compound having a pKb of 1 or less is more preferable. Specifically, it is preferable to use at least one selected from the group consisting of hydroxides of alkali metals or alkaline earth metals, and acetates of alkali metals or alkaline earth metals, and hydroxides of alkali metals or alkaline earth metals are used. It is more preferable to do, and it is more preferable to use sodium hydroxide. A basic compound can be used individually by 1 type or in combination of 2 or more types.

The concentration of the basic compound contained in the basic aqueous solution is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass, based on the total mass of the basic aqueous solution from the viewpoint of more suppressing the generation of acid. % Or more is more preferred. The concentration of the basic compound contained in the basic aqueous solution is preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total mass of the basic aqueous solution, from the viewpoint of preventing particle coarsening. And 15% by mass or less is more preferable.

The amount of the basic compound contained in the basic aqueous solution is 100 parts by mass based on 100 parts by mass of the amount of the compound that generates an acid by reacting with water contained in the mixture added to the basic aqueous solution from the viewpoint of more sufficiently suppressing the generation of acid. Above are preferable, 200 mass parts or more are more preferable, and 300 mass parts or more are still more preferable. The amount of the basic compound contained in the basic aqueous solution is 600 parts by mass or less with respect to 100 parts by mass of the amount of the compound that generates an acid by reacting with water contained in the mixture added to the basic aqueous solution from the viewpoint of preventing coarsening of particles. Is preferable, 500 parts by mass or less are more preferable, and 400 parts by mass or less are still more preferable.

The pH of the basic aqueous solution at 25°C is preferably 8 or more, more preferably 10 or more, and still more preferably 13 or more from the viewpoint of suppressing the generation of acid. The basic aqueous solution may have a pH of 14 or less at 25°C.

The temperature of the basic aqueous solution is preferably 1° C. or higher, more preferably 5° C. or higher, and still more preferably 10° C. or higher from the viewpoint of suppressing the generation of acid. The temperature of the basic aqueous solution is preferably 90°C or less, more preferably 60°C or less, and still more preferably 30°C or less, from the viewpoint of preventing coarsening of particles.

The amount of basic aqueous solution used is preferably 500 parts by mass or more, and 800 parts by mass with respect to 100 parts by mass of the mixture containing a compound that generates an acid by reacting with zinc halide phthalocyanine and water from the viewpoint of sufficiently depositing zinc halide phthalocyanine. More preferably, more than 1000 parts by mass or more are more preferable. The amount of basic aqueous solution used is 5000 parts by mass or less based on 100 parts by mass of a mixture containing a zinc halide phthalocyanine and a compound that generates an acid by reacting with water from the viewpoint of peptizing the agglomerated particles by high shear force. It is preferable, and 3000 parts by mass or less are more preferable, and 2000 parts by mass or less are still more preferable.

It is preferable that the first step further includes a post-treatment step of post-treating the precipitate after the precipitation step.

The first step may further include, for example, a step of filtering the precipitate (first post-treatment step). The first post-treatment step may be a step of filtering and washing the precipitate, or a step of filtering, washing, and drying the precipitate. Washing may be performed using, for example, an aqueous solvent such as water, aqueous sodium hydrogen sulfate, aqueous sodium hydrogen carbonate or aqueous sodium hydroxide. In washing, if necessary, an organic solvent such as acetone, toluene, methyl alcohol, ethyl alcohol, or dimethylformamide may be used. For example, after washing with an aqueous solvent, washing with an organic solvent may be performed. Washing may be repeated a plurality of times (for example, 2 to 5 times). Specifically, washing is preferably performed until the pH of the filtrate becomes equal to the pH of water used for washing (for example, the difference between the two is 0.2 or less).

The first step may further include, for example, a step of dry grinding the precipitate (second post-treatment step). Dry grinding may be performed in a crusher such as an attritor, a ball mill, a vibration mill, or a vibration ball mill. Dry grinding may be performed while heating (for example, while heating so that the temperature inside the grinder becomes 40°C to 200°C). After dry grinding, you may wash with water. By washing with water after dry grinding (particularly after dry grinding with an attritor), the amount of acid contained in the crude pigment can be further reduced. The washing may be either water washing (washing with water of less than 40°C) or hot water washing (washing with water of 40°C or more). Washing is preferably performed until the pH of the filtrate becomes equal to the pH of the water used for washing (for example, the difference between them is 0.2 or less), similar to the first post-treatment step. Further, at or before washing with water, a treatment for improving the wettability of the precipitate (for example, a treatment for bringing the precipitate into contact with a water-soluble organic solvent such as methanol) may be performed. Dry grinding and washing may be repeated a plurality of times.

The first step may further include, for example, a step of kneading the precipitate with water (third post-treatment step). By performing the third post-treatment process, the amount of acid contained in the crude pigment can be further reduced. Kneading can be performed using, for example, a kneader or a mixmuller. Kneading may be performed while heating. For example, the water temperature may be 40°C or higher. An inorganic salt may be added to water. At this time, by presenting at least a part of the inorganic salt in a solid state, the force applied during kneading can be improved. When kneading, an organic solvent (e.g., an organic solvent that can be used in the second step described later) may be used, but the amount of the organic solvent is preferably less than that of water, and more preferably no organic solvent. . After kneading, washing may be performed in the same manner as in the first post-treatment process. Kneading and washing may be repeated a plurality of times.

The first step may further include, for example, a step of heating the precipitate in water (for example, boiling (fourth post-treatment step)). By performing a fourth post-treatment step, the crude pigment is treated with It is possible to further reduce the amount of acid contained in. The heating temperature in water may be, for example, 40° C. or higher and the boiling point or lower, and the heating time may be, for example, 1 to 300 minutes. An organic solvent (for example, an organic solvent that can be used in the second step described later) may be mixed, but the mixed amount of the organic solvent is preferably 20 parts by mass or less based on 100 parts by mass of water. In the treatment step, from the viewpoint of further removing the acid, washing may be performed after heating the precipitate in water, washing after heating the precipitate in water, and heating and washing in water one or more times (preferably 2 or more times) may be further repeated, and washing may be performed in the same manner as in the first post-treatment step.

In this embodiment, two or more of the above-described first to fourth post-treatment steps may be performed. In the case of performing two or more steps in the first to fourth post-treatment steps, the order is not particularly limited.

By the first step, a zinc halide phthalocyanine crude pigment is obtained, but as described above, in the present embodiment, the precipitate obtained in the first step may be directly used as a zinc halide phthalocyanine crude pigment. What performed the treatment step (at least one step in the first to fourth post treatment steps) may be used as a zinc halide phthalocyanine crude pigment.

The zinc halide phthalocyanine crude pigment obtained in the first step contains one type or a plurality of types of halogenated zinc phthalocyanines having different numbers of halogen atoms.

In one embodiment, the average of the number of bromine atoms in one molecule of the compound represented by formula (1) in the crude zinc halide phthalocyanine pigment is less than 13. The average number of bromine atoms may be 12 or less or 11 or less. The average number of bromine atoms may be 0.1 or more, 6 or more, or 8 or more. The above-described upper and lower limits can be arbitrarily combined. For example, the average number of bromine atoms may be 0.1 to less than 13, 8 to 12 or 8 to 11. Moreover, also in the following description, the upper limit value and the lower limit value individually stated can be combined arbitrarily.

When the average number of bromine atoms is less than 13, the average number of halogen atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine crude pigment is 14 or less, 13 or less, 13 It may be less than or less than 12. The average number of halogen atoms is 0.1 or more, and may be 8 or more or 10 or more.

When the average number of bromine atoms is less than 13, the average number of chlorine atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine crude pigment is 5 or less, 3 or less, 2.5 It may be less than or less than two. The average number of chlorine atoms may be 0.1 or more, 0.3 or more, 0.6 or more, 0.8 or more, 1 or more, 1.3 or more, or 2 or more.

In another embodiment, the average of the number of bromine atoms in one molecule of the compound represented by the formula (1) in the zinc halide phthalocyanine crude pigment is 13 or more. The average number of bromine atoms may be 14 or more. The average number of bromine atoms may be 15 or less.

When the average number of bromine atoms is 13 or more, the average number of halogen atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine crude pigment is 13 or more, 14 or more, or 15 It may be more. The average number of halogen atoms is 16 or less and may be 15 or less.

When the average number of bromine atoms is 13 or more, the average number of chlorine atoms in one molecule of the compound represented by the formula (1) in the zinc halide phthalocyanine crude pigment may be 0.1 or more or 1 or more. The average number of chlorine atoms may be three or less or less than two.

The number of halogen atoms (e.g., the number of bromine atoms and the number of chlorine atoms) is determined by, for example, a matrix-assisted laser desorption ionization time-of-flight mass spectrometer (JMS-S3000 manufactured by Nippon Electric Corporation). It can be specified by mass spectrometry of the used zinc halide phthalocyanine crude pigment. Specifically, the number of each halogen atom can be calculated as a relative value per zinc atom from the mass ratio of the zinc atom and each halogen atom in the zinc halide phthalocyanine crude pigment.

The arithmetic standard deviation of the particle size distribution of the zinc halide phthalocyanine crude pigment is, for example, 15 nm or more. The arithmetic standard deviation of the particle size distribution of the zinc halide phthalocyanine crude pigment is, for example, 1500 nm or less. When the arithmetic standard deviation of the particle size distribution of the zinc halide phthalocyanine crude pigment is in such a range, finer pigment particles are easily obtained. The arithmetic standard deviation of the particle size distribution of the zinc halide phthalocyanine crude pigment can be measured using a dynamic light scattering particle size distribution measuring device, and specifically, it can be measured in the following methods and conditions.

<Method>

Zircon beads of 0.3 to 0.4 mm were used together with 2.48 g of zinc halide phthalocyanine crude pigment, 1.24 g of BYK-LPN6919 manufactured by Big Chemical, 1.86 g of Unidic ZL-295 manufactured by DIC, and 10.92 g of propylene glycol monomethyl ether acetate. Then, it disperses for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a dispersion. 0.02 g of the dispersion after removing the zircon beads with a nylon mesh was diluted with 20 g of propylene glycol monomethyl ether acetate to obtain a dispersion for measuring particle size distribution.

<condition>

Measurement equipment: Dynamic light scattering particle size distribution measuring device LB-550 (manufactured by Horiba Seisakujo Co., Ltd.)

·Measurement temperature: 25℃

·Measurement sample: dispersion for particle size distribution measurement

Data analysis conditions: scattered light intensity based on particle diameter, dispersion medium refractive index 1.402

The zinc halide phthalocyanine crude pigment obtained in this embodiment has a smaller amount of the acid contained as compared to the conventional crude pigment. Therefore, the pH of the zinc halide phthalocyanine crude pigment is, for example, 4.0 or higher. Here, the pH of the zinc halide phthalocyanine crude pigment is, after mixing 5 g of the zinc halide phthalocyanine crude pigment with 5 g of methanol, and further mixing with 100 ml of ion-exchanged water, and heating the obtained mixture for 5 minutes to boil it, and for 5 more minutes. After heating to maintain the boiled state, cooling the mixture after heating to 30°C or less, adjusting the total amount of the mixture to 100 ml with ion-exchanged water, filtering, and measuring the pH of the obtained filtrate at 25°C. I can. The pH of the zinc halide phthalocyanine crude pigment is preferably 5.0 or more, more preferably 5.5 or more, still more preferably 6.0 or more, and particularly preferably 6.5 or more, from the viewpoint of easy obtaining finer pigment particles. to be. The pH of the zinc halide phthalocyanine crude pigment is, for example, 8.5 or less, and may be 8.0 or less or 7.5 or less.

The zinc halide phthalocyanine crude pigment may contain aluminum-containing components such as aluminum hydroxide when a compound containing aluminum halide is used in, for example, a melting method. However, since the aluminum-containing component may cause a decrease in contrast, the smaller the amount of aluminum (the amount of Al) in the zinc halide phthalocyanine crude pigment, the more preferable. From such a viewpoint, the amount of Al contained in the zinc halide phthalocyanine crude pigment is preferably 3000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 1000 mass ppm or less. The amount of Al contained in the zinc halide phthalocyanine crude pigment can be determined by a high frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy). Moreover, when a strong basic basic aqueous solution is used in the precipitation step in the first step, since aluminum hydroxide can be dissolved and removed, there is a tendency that the amount of Al can be reduced.

In the second step, for example, a zinc halide phthalocyanine crude pigment is kneaded and ground to refine it. Kneading can be performed using, for example, a kneader or a mixed muller.

The second step may be a step of kneading a zinc halide phthalocyanine crude pigment together with an organic solvent, or may be a step of kneading together with an inorganic salt and an organic solvent. In the second step, it is preferable not to use water. The amount of water used may be, for example, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, based on 100 parts by mass of the zinc halide phthalocyanine crude pigment.

As the organic solvent, a zinc halide phthalocyanine crude pigment and an inorganic salt that do not dissolve can be used. As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth. As such an organic solvent, a water-soluble organic solvent can be used suitably. As an organic solvent, for example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy )Ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2 -Propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and the like can be used. The amount of the organic solvent (for example, a water-soluble organic solvent) is not particularly limited, but is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the zinc halide phthalocyanine crude pigment.

In the second step, the zinc halide phthalocyanine crude pigment may be kneaded while heating. The heating temperature is preferably 40° C. or higher, more preferably 60° C. or higher, further preferably 80° C. or higher, and particularly preferably 90° C. or higher, from the viewpoint of making it easier to obtain finer pigment particles. . The heating temperature may be, for example, 150°C or less.

The kneading time in the second step may be, for example, 1 to 60 hours.

In the second step, when an inorganic salt and an organic solvent are used, a mixture containing a halogenated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent is obtained, but the organic solvent and inorganic salt are removed from the mixture and halogenated as necessary. Operations such as washing, filtration, drying, pulverization, etc. may be performed on a solid substance mainly composed of a zinc phthalocyanine pigment.

For washing, both water washing and hot water washing can be employed. Washing may be repeatedly performed in the range of 1 to 5 times. When a water-soluble inorganic salt and a water-soluble organic solvent are used, the organic solvent and the inorganic salt can be easily removed by washing with water. If necessary, acid washing, alkali washing, and organic solvent washing may be performed.

Examples of drying after washing and filtration include batch or continuous drying in which pigments are dehydrated and/or desolvated by heating at 80 to 120° C. by a heating source installed in a dryer. . As a dryer, in general, a box-type dryer, a band dryer, a spray dryer, etc. are mentioned. In particular, spray dry drying using a spray dryer is preferable because it is heterodisperse during paste production.

The pulverization after drying is not an operation to increase the specific surface area or decrease the average particle diameter of the primary particles, but when the pigment becomes lamp-like, such as in the case of drying using a box-type dryer or a band dryer, It is done to loosen and powder. For example, pulverization by mortar, hammer mill, disk mill, pin mill, jet mill, etc. are mentioned.

According to the above production method, a fine zinc halide phthalocyanine pigment can be obtained. The present inventors infer the reason for obtaining such an effect as follows. First of all, when an acid is present during pigmentation, since the acid promotes aggregation of the particles, the refinement of the pigment particles is inhibited. On the other hand, in the above production method, since the inclusion of the acid in the crude pigment is suppressed, the effect of the above acid can be alleviated. Therefore, according to the method, a fine zinc halide phthalocyanine pigment is obtained.

The zinc halide phthalocyanine pigment obtained by the above production method is suitably used as a green pigment for color filters. In general, as the particles of the pigment used in the pixel portion of the color filter are smaller, the contrast and brightness tend to improve. Therefore, when the zinc halide phthalocyanine pigment obtained by the above production method is used as a green pigment for color filters, excellent contrast tends to be obtained, and excellent luminance tends to be obtained.

The average particle diameter (average primary particle diameter) of the primary particles of the zinc halide phthalocyanine pigment obtained by the above method is, for example, 30 nm or less. According to the above method, for example, a zinc halide phthalocyanine pigment having an average primary particle diameter of 25 nm or less can also be obtained. The average primary particle diameter of the zinc halide phthalocyanine pigment may be 10 nm or more. Here, the average primary particle diameter is an average value of the major diameters of the primary particles, and can be obtained by measuring the major diameter of the primary particles in the same manner as the measurement of the average aspect ratio described later.

The average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, 1.2 or more, 1.3 or more, 1.4 or more, or 1.5 or more. The average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, less than 2.0, 1.8 or less, 1.6 or less, or 1.4 or less. According to a zinc halide phthalocyanine pigment having such an average aspect ratio, a more excellent contrast can be obtained.

The zinc halide phthalocyanine pigment having an average aspect ratio of primary particles in the range of 1.0 to 3.0 preferably does not contain primary particles having an aspect ratio of 5 or more, and more preferably does not contain primary particles having an aspect ratio of 4 or more. It is more preferable that the primary particles having an aspect ratio of more than 3 are not included.

The aspect ratio and the average aspect ratio of the primary particles can be measured by the following method. First, particles in the field of view are photographed with a transmission electron microscope (for example, JEM-2010 manufactured by Nippon Electric Corporation). Then, the longer diameter (longer diameter) and shorter diameter (shorter diameter) of the primary particles present on the two-dimensional image are measured, and the ratio of the longer diameter to the shorter diameter is taken as the aspect ratio of the primary particles. Further, for 40 primary particles, the average value of the long and short diameters is calculated, and the ratio of the long diameter to the short diameter is calculated using these values, and this is taken as the average aspect ratio. At this time, the zinc halide phthalocyanine pigment, which is a sample, is ultrasonically dispersed in a solvent (eg, cyclohexane) and then photographed under a microscope. Further, instead of the transmission electron microscope, a scanning electron microscope may be used.

In the above production method, aggregation of the pigment can be suppressed, and since the primary particles of the pigment can be made small, the surface area capable of adsorbing a base can be increased. Therefore, in the above production method, a zinc halide phthalocyanine pigment having a large amount of base adsorption can be obtained. In the dispersion of zinc halide phthalocyanine pigments, dispersants having basic functional groups (e.g., primary to tertiary amino groups) as adsorbents to the pigment are widely used, but when the amount of base adsorption of zinc halide phthalocyanine pigments is large, the amount of these dispersants is used. Can be reduced. Therefore, according to the zinc halide phthalocyanine pigment having a large amount of base adsorption, the dispersant having a lower heat resistance than the pigment decomposes by heat around 200°C applied at the time of manufacturing the color filter, thereby reducing the contrast and brightness, and the dispersant is Since it is insoluble, it is possible to reduce defects such as a decrease in resolution and developability, and a color filter thickening by a dispersant that is a non-colored component.

Further, in the above production method, the amount of Al contained in the zinc halide phthalocyanine crude pigment can be reduced by using a strongly basic basic aqueous solution in the precipitation step in a melting method or the like. Usually, since the amount of Al does not change during pigmentation, the zinc halide phthalocyanine pigment having a large amount of base adsorption and a small amount of Al tends to be obtained from the zinc halide phthalocyanine crude pigment having a small Al content. For example, a zinc halide phthalocyanine pigment having a base adsorption amount of 0.13 mol/kg or more and an Al content of 3000 mass ppm or less can be obtained.

The base adsorption amount of the zinc halide phthalocyanine pigment is preferably 0.13 mol/kg or more, more preferably 0.135 mol/kg or more, and still more preferably 0.140 mol/kg or more. The base adsorption amount of the zinc halide phthalocyanine pigment may be 0.160 mol/kg or less. The amount of base adsorption was measured by the method of Examples.

The Al content in the zinc halide phthalocyanine pigment becomes like this. Preferably it is 3000 mass ppm or less, More preferably, it is 2000 mass ppm or less, More preferably, it is 1000 mass ppm or less, Especially preferably, it is less than 1000 mass ppm. The amount of Al contained in the zinc halide phthalocyanine pigment can be determined by a high frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy).

(Example)

Hereinafter, the content of the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited to the following examples.

<Example 1>

[Synthesis of crude pigment]

To a 300 ml flask, 91 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), aluminum chloride (manufactured by Kanto Chemical Corporation) 109 g, sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 15 g, 30 g of zinc phthalocyanine (manufactured by DIC Corporation) and 230 g of bromine (manufactured by Fujifilm Wako Junyaku Kogyo Corporation) were added. The temperature was raised to 130°C and maintained at 130°C for 40 hours. The reaction mixture was taken out to 2500 g of aqueous sodium hydroxide (NaOH) solution having a liquid temperature of 15°C and a concentration of 10% by mass, followed by filtration, washing with water, and drying to obtain a zinc halide phthalocyanine crude pigment (crude pigment A1). In addition, washing with water was performed until the difference between the pH of the filtrate and the pH of water used for washing became ±0.2.

The crude pigment A1 was subjected to mass spectrometry by JMS-S3000 manufactured by Nippon Denshi Co., Ltd., and it was confirmed that the average chlorine number of zinc halide phthalocyanine (P1) constituting the crude pigment A1 was 1.8 and the average bromine number was 13.2. Further, the Delay Time at the time of mass spectrometry was 500 ns, the Laser Intensity was 44%, and the Resolving Power Value of the peak of m/z=1820 or more and 1860 or less was 32111.

[Measurement of pH of crude pigment A1]

In a 300 ml beaker, 5 g of crude pigment A1 and 5 g of methanol were weighed and mixed, and then 100 ml of ion-exchanged water was further weighed and boiled over 5 minutes with a hot stirrer, and boiling was continued for 5 minutes. Next, after standing to cool to 30°C or less, it was transferred to a 100 ml measuring cylinder, and the total amount was adjusted to 100 ml with ion-exchanged water, and then filtered. When the pH and specific conductivity of the filtrate were measured, the pH of the crude pigment A1 at 25°C was 7.8, and the specific conductivity was 67 μS/cm (microsiemens per centimeter). In addition, the pH was measured with a PH71 personal pH meter manufactured by Yokogawa Electric Co., Ltd., and the specific conductivity was measured with Seven Easy S30 manufactured by METTLER TOLEDO Corporation.

[Measurement of Al (aluminum) amount in crude pigment A1]

0.25 g of crude pigment A1 was mixed with 5 ml of nitric acid, irradiated with microwave to decompose, and then determined to 25 ml with ion-exchanged water. 6 kinds of nitric acid of 0 mass ppm, 1000 mass ppm, 2000 mass ppm, 5000 mass ppm, 10000 mass ppm, and 100000 mass ppm by adding nitric acid at the same level as the pigment decomposition to the aluminum standard solution for ICP emission spectroscopy analysis A sample for production of a calibration curve was prepared, and the amount of Al was measured with an ICP spectroscopic analyzer (manufactured by Perkin Elmer, Optima 4300DV) to prepare a calibration curve. The solution composed of the pigment decomposition product was also measured with an ICP spectroscopic analyzer, and the amount of Al in the crude pigment A1 was calculated from the calibration curve, and the amount of Al was not more than 1000 ppm by mass.

[Pigmentation]

40 g of crude pigment A1, 400 g of pulverized sodium chloride, and 63 g of DEG (diethylene glycol) were put into a twin arm kneader, and kneaded at 80°C for 8 hours. The mixture after kneading was taken out into 2 kg of water at 80°C and stirred for 1 hour. Thereafter, it was filtered, washed with hot water, dried and pulverized to obtain a green pigment G1.

[Measurement of average primary particle diameter]

Green pigment G1 was ultrasonically dispersed in cyclohexane, and then photographed under a microscope, and the average particle diameter (average primary particle diameter) of the primary particles was calculated from the average value of 40 primary particles constituting the aggregate on the two-dimensional image. The average particle diameter of the primary particles was 24 nm.

[Measurement of pH of green pigment G1]

In a 300 ml beaker, 5 g of green pigment G1 and 5 g of methanol were weighed and mixed, and then 100 ml of ion-exchanged water was further weighed and boiled over 5 minutes with a hot stirrer, and boiling was continued for 5 minutes. Next, after standing to cool to 30°C or less, it was transferred to a 100 ml measuring cylinder, and the total amount was adjusted to 100 ml with ion-exchanged water, and then filtered. When the pH and specific conductivity of the filtrate were measured, the pH at 25°C was 7.6 and the specific conductivity was 59 μS/cm.

[Measurement of Al (aluminum) amount in green pigment G1]

Except having used the green pigment G1 in place of the crude pigment A1, it carried out similarly to the Al amount measurement in the crude pigment A1, and calculated the Al amount in green pigment G1. Al amount was 1000 mass ppm or less.

[Measurement of base adsorption amount]

The amount of base adsorption of green pigment G1 was measured using an automatic titration apparatus COM-1700 (manufactured by Hitachi High-Tech Science Corporation). Specifically, first, about 0.1 g of green pigment G1 was mixed and stirred with 15 mL of a base solution for adsorption with a conditioning mixer (2000 rpm, 3 minutes). After sedimentation of green pigment G1 by centrifugation (11000 rpm, 20 minutes), 10 mL of the supernatant was aliquoted, and potentiometric titration of the liquid diluted with 50 mL of n-propyl acetate (NPAC) was performed. The amount of non-adsorbed base present in the solution was measured. The amount of base adsorption to the green pigment G1 was calculated by subtracting the determined amount of unadsorbed base from the added amount of base. In addition, as the base solution for adsorption, 0.001 mol/L tetran-butylammonium hydroxide (TBAH)/NPAC solution was used, and as the acid solution for titration, 0.001 mol/L p-toluenesulfonic acid (PTSA)/NPAC solution was used. Used.

[Evaluation of contrast and luminance]

Pigment Yellow 138 (Chromophane Yellow 6206EC manufactured by Dainichi Corporation) 1.65 g, DISPERBYK-161 (manufactured by Vic Chemical Corporation) 3.85 g, propylene glycol monomethyl ether acetate 11.00 g, and 0.3 to 0.4 mm zircon beads It was used and dispersed for 2 hours with a Toyo Seiki Co., Ltd. paint shaker to obtain a dispersion.

4.0 g of the dispersion, 0.98 g of Unidic ZL-295, and 0.22 g of propylene glycol monomethyl ether acetate were added, and mixed with a paint shaker to obtain a yellow composition (TY1) for color toning.

2.48 g of the green pigment G1 obtained in Example 1 was combined with 1.24 g of BYK-LPN6919 manufactured by Big Chemical, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate, along with a zircon of 0.3 to 0.4 mm. Using beads, it dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a pigment dispersion for color filters (MG1).

Add 4.0 g of the pigment dispersion for color filter (MG1), 0.98 g of Unidic ZL-295 manufactured by DIC Corporation, 0.22 g of propylene glycol monomethyl ether acetate, and mix with a paint shaker to form a green pixel part for a color filter. The composition for evaluation (CG1) was obtained.

The composition for evaluation (CG1) was spin-coated on a soda glass substrate, dried at 90°C for 3 minutes, and then heated at 230°C for 1 hour. Thereby, the glass substrate for contrast evaluation which has the colored film on the soda glass substrate was produced. Further, by adjusting the spin rotation speed during spin coating, the thickness of the colored film obtained by heating at 230° C. for 1 hour was set to 1.8 μm.

In addition, the coating solution obtained by mixing the toning yellow composition (TY1) and the evaluation composition (CG1) prepared above was spin-coated on a soda glass substrate, dried at 90°C for 3 minutes, and heated at 230°C for 1 hour. did. Thereby, a glass substrate for luminance evaluation having a colored film on a soda glass substrate was produced. In addition, by adjusting the mixing ratio of the toning yellow composition (TY1) and the evaluation composition (CG1) and the spin rotation speed during spin coating, the chromaticity in the C light source of the colored film obtained by heating at 230°C for 1 hour ( A colored film having x, y) of (0.275, 0.570) was produced.

The contrast of the colored film in the glass substrate for contrast evaluation was measured with a contrast tester CT-1 manufactured by Tsubosaka Denki Co., Ltd., and the luminance of the colored film in the glass substrate for brightness evaluation was measured with U-3900 manufactured by Hitachi High-Tech Science Corporation. Measured. Table 1 shows the results. In addition, the contrast and luminance shown in Table 1 are values based on the contrast and luminance of Comparative Example 1.

<Examples 2 and 3>

When synthesizing the crude pigment, in the same manner as in Example 1, except that an aqueous solution of sodium acetate (CH ₃ COONa) or an aqueous solution of sodium hydrogen carbonate (NaHCO ₃ ) was used instead of an aqueous sodium hydroxide solution as the extraction liquid. Pigments A2 and A3 were obtained. As a result of mass spectrometry for the crude pigments A2 and A3 by JMS-S3000 manufactured by Nihon Denshi Co., Ltd., all crude pigments were composed of zinc halide phthalocyanine (P1) having an average chlorine number of 1.8 and an average bromine number of 13.2. Confirmed that. Further, in the same manner as in Example 1, the pH and specific conductivity of the crude pigments A2 and A3, and the amount of Al in the crude pigments A2 and A3 were measured. Table 1 shows the results.

Green pigments G2 and G3 were obtained in the same manner as in Example 1 except that the crude pigment A2 or A3 was used respectively instead of the crude pigment A1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigments G2 and G3 were measured. In addition, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced in the same manner as in Example 1 except that the green pigment G2 or G3 was used instead of the green pigment G1, and the contrast and brightness were measured. Table 1 shows the results.

<Examples 4 to 8>

At the time of synthesis of the crude pigment, crude pigments A4 to A8 were obtained in the same manner as in Example 1, except that the concentration of the sodium hydroxide aqueous solution as the extraction liquid was changed to the value shown in Table 1. As a result of mass spectrometry for the crude pigments A4 to A8 by JMS-S3000 manufactured by Nihon Denshi Co., Ltd., all crude pigments were composed of zinc halide phthalocyanine (P1) having an average chlorine number of 1.8 and an average bromine number of 13.2. Confirmed that. Further, in the same manner as in Example 1, the pH and specific conductivity of the crude pigments A4 to A8, and the amount of Al in the crude pigments A4 to A8 were measured. Table 1 shows the results.

Green pigments G4 to G8 were obtained in the same manner as in Example 1 except that the crude pigments A4 to A8 were used respectively instead of the crude pigment A1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigments G4 to G8 were measured. Further, in the same manner as in Example 1 except that the green pigments G4 to G8 were respectively used instead of the green pigment G1, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced, and the contrast and brightness were measured. Table 1 shows the results.

<Examples 9 and 10>

At the time of synthesis of the crude pigment, crude pigments A9 and A10 were obtained in the same manner as in Example 1, except that the temperature of the sodium hydroxide aqueous solution as the extraction liquid was changed to the value shown in Table 1. As a result of mass spectrometry for the crude pigments A9 and A10 by JMS-S3000 manufactured by Nihon Denshi Co., Ltd., all crude pigments were composed of zinc halide phthalocyanine (P1) having an average chlorine number of 1.8 and an average bromine number of 13.2. Confirmed that. Further, in the same manner as in Example 1, the pH and specific conductivity of the crude pigments A9 and A10, and the amount of Al in the crude pigments A9 and A10 were measured. Table 1 shows the results.

Green pigments G9 and G10 were obtained in the same manner as in Example 1 except that the crude pigment A9 or A10 was used instead of the crude pigment A1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigments G9 and G10 were measured. Further, in the same manner as in Example 1 except that the green pigment G9 or G10 was used instead of the green pigment G1, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were prepared, and the contrast and brightness were measured. Table 1 shows the results.

<Examples 11 and 12>

Green pigments G11 and G12 were obtained, respectively, in the same manner as in Example 1, except that the heating temperature and/or the kneading time at the time of kneading in the pigmentation step were changed as shown in Table 1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigments G11 and G12 were measured. In addition, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced in the same manner as in Example 1 except that the green pigment G11 or G12 was used instead of the green pigment G1, and the contrast and luminance were measured. Table 1 shows the results.

<Comparative Examples 1 and 2>

At the time of synthesis of the crude pigment, crude pigments A13 and A14 were obtained in the same manner as in Example 1, except that water or hydrochloric acid (aqueous HCl solution) having a concentration of 10% by mass was used instead of an aqueous sodium hydroxide solution as an extraction liquid. As a result of mass spectrometry for the crude pigments A13 and A14 by JMS-S3000 manufactured by Nihon Denshi Co., Ltd., all crude pigments were composed of zinc halide phthalocyanine (P1) having an average chlorine number of 1.8 and an average bromine number of 13.2. Confirmed that. In the same manner as in Example 1, the pH and specific conductivity of the crude pigments A13 and A14, and the amount of Al in the crude pigments A13 and A14 were measured. Table 1 shows the results.

Green pigments G13 and G14 were obtained in the same manner as in Example 1 except that the crude pigment A13 or A14 was used instead of the crude pigment A1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigments G13 and G14 were measured. In addition, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced in the same manner as in Example 1 except that the green pigment G13 or G14 was used instead of the green pigment G1, and the contrast and brightness were measured. Table 1 shows the results.

<Example 13>

In a 300 ml flask, 90 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 27 g of zinc phthalocyanine (manufactured by DIC Corporation) and 55 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. The temperature was raised to 130°C and maintained at 130°C for 40 hours. The reaction mixture was taken out to 2500 g of sodium hydroxide (NaOH) aqueous solution having a liquid temperature of 15°C and a concentration of 10% by mass, followed by filtration, washing with water, and drying to obtain a zinc halide phthalocyanine crude pigment (crude pigment A15). In addition, washing with water was performed until the pH of the filtrate became a pH equivalent to that of water used for washing.

The crude pigment A15 was subjected to mass spectrometry by JMS-S3000 manufactured by Nihon Denshi Corporation, and it was confirmed that the average number of chlorine halide phthalocyanine (P2) constituting the crude pigment A15 was 2.9 and the average bromine number was 9.3. In mass spectrometry, the Delay Time was 510 ns, the Laser Intensity was 40%, and the Resolving Power Value of the peak of m/z=1820 or more and 1860 or less was 65086. Further, in the same manner as in Example 1, the pH and specific conductivity of the crude pigment A15, and the amount of Al in the crude pigment A16 were measured. The results are shown in Table 2.

A green pigment G15 was obtained in the same manner as in Example 1 except that the crude pigment A15 was used instead of the crude pigment A1. Further, in the same manner as in Example 1, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigment G15 were measured. In addition, Pigment Yellow 185 (Paliotol Yellow D1155 manufactured by BASF) was used in place of Pigment Yellow 138 (Chromophane Yellow 6206EC manufactured by Dainichi Corporation), and the green pigment G15 was used instead of the green pigment G1, and, Except having adjusted the chromaticity (x, y) of the colored film to (0.230, 0.670), it carried out similarly to Example 1, the glass substrate for contrast evaluation and the glass substrate for brightness evaluation were produced, and the contrast and brightness were measured. The results are shown in Table 2.

<Comparative Example 3>

At the time of synthesis of the crude pigment, a crude pigment A16 was obtained in the same manner as in Example 13, except that water was used instead of the aqueous sodium hydroxide solution as the extraction liquid. As a result of performing mass spectrometry for crude pigment A16 by JMS-S3000 manufactured by Nihon Denshi, it was confirmed that all crude pigments were composed of zinc halide phthalocyanine (P2) having an average chlorine number of 2.9 and an average bromine number of 9.3. did. Further, in the same manner as in Example 13, the pH and specific conductivity of the crude pigment A16, and the amount of Al in the crude pigment A16 were measured. The results are shown in Table 2.

A green pigment G16 was obtained in the same manner as in Example 13 except that the crude pigment A16 was used instead of the crude pigment A15. Further, in the same manner as in Example 13, the average primary particle diameter, pH, specific conductivity, Al amount, and base adsorption amount of the green pigment G17 were measured. Moreover, in the same manner as in Example 13, except that the green pigment G16 was used instead of the green pigment G15, a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced, and the contrast and brightness were measured. The results are shown in Table 2.

[Table 1]

[Table 2]

Claims (7)

A step of obtaining a zinc halide phthalocyanine crude pigment by taking out and depositing a zinc halide phthalocyanine synthesized using a compound that generates an acid by reacting with water in a basic aqueous solution; and
A method for producing a zinc halide phthalocyanine pigment having a step of pigmenting the zinc halide phthalocyanine crude pigment. The method of claim 1,
The production method, wherein the concentration of the basic compound contained in the basic aqueous solution is 1% by mass or more. The method according to claim 1 or 2,
The production method, wherein the basic aqueous solution contains a hydroxide of an alkali metal or an alkaline earth metal. The method according to any one of claims 1 to 3,
The production method, wherein the temperature of the basic aqueous solution is 5 to 90°C. The method according to any one of claims 1 to 4,
The production method, wherein the pH of the zinc halide phthalocyanine crude pigment is 5.0 or higher. The method according to any one of claims 1 to 5,
The production method, wherein the amount of Al contained in the zinc halide phthalocyanine crude pigment is 3000 mass ppm or less. A zinc halide phthalocyanine pigment having a base adsorption amount of 0.13 mol/kg or more and an Al content of 3000 mass ppm or less.